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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Anionic Chain-Growth Polymerization: Mechanism01:04

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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Cationic Chain-Growth Polymerization: Mechanism00:57

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Step-Growth Polymerization: Overview01:03

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Polymers02:34

Polymers

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The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
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Aromatic Gain in a Supramolecular Polymer.

Victorio Saez Talens1, Pablo Englebienne2, Thuat T Trinh3

  • 1Department of Supramolecular and Biomaterials Chemistry, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden (The Netherlands).

Angewandte Chemie (International Ed. in English)
|July 17, 2015
PubMed
Summary

This study reveals how aromaticity and hydrogen bonding in supramolecular polymers create stable, fibrous materials. This synergy enhances material properties, offering new possibilities for advanced polymer design.

Keywords:
aromaticitynon-covalent interactionsself-assemblysquaramidessupramolecular polymers

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Area of Science:

  • Supramolecular Chemistry
  • Polymer Science
  • Materials Science

Background:

  • Supramolecular polymers self-assemble via non-covalent interactions.
  • Aromaticity and hydrogen bonding are key interaction types in molecular assembly.
  • Controlling aggregate morphology and stability is crucial for material applications.

Purpose of the Study:

  • To explore the synergistic effects of aromatic gain and hydrogen bonding in supramolecular polymers.
  • To design and synthesize partially aromatic bis(squaramide) bolaamphiphiles.
  • To investigate the self-assembly behavior and resulting material properties.

Main Methods:

  • UV-Vis and IR spectroscopy to analyze electronic and geometric changes.
  • Computational methods including NICS and HOMA indices to quantify aromaticity.
  • Synthesis and characterization of bis(squaramide) bolaamphiphiles and their aggregates.

Main Results:

  • Self-assembly into stiff, high-aspect-ratio fibers driven by hydrophobic, hydrogen-bonding, and aromatic effects.
  • Evidence of strong hydrogen bonding and significant aromatic gain (≥30% in pentamer) upon polymerization.
  • Demonstrated synergy between aromatic gain and hydrogen bonding leading to enhanced thermodynamic stability and altered aggregate morphology.

Conclusions:

  • The combination of aromatic gain and hydrogen bonding is a powerful strategy for designing stable supramolecular polymers.
  • This synergy significantly impacts the thermodynamic stability and morphology of self-assembled fibers.
  • The findings provide insights into molecular design for advanced materials with tailored properties.